EP2785780A1 - Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof - Google Patents

Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Info

Publication number
EP2785780A1
EP2785780A1 EP12839189.3A EP12839189A EP2785780A1 EP 2785780 A1 EP2785780 A1 EP 2785780A1 EP 12839189 A EP12839189 A EP 12839189A EP 2785780 A1 EP2785780 A1 EP 2785780A1
Authority
EP
European Patent Office
Prior art keywords
amine
composition
additive composition
polymerization
aromatic vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12839189.3A
Other languages
German (de)
French (fr)
Other versions
EP2785780B1 (en
Inventor
Mahesh Subramaniyam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dorf Ketal Chemicals India Pvt Ltd
Original Assignee
Dorf Ketal Chemicals India Pvt Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dorf Ketal Chemicals India Pvt Ltd filed Critical Dorf Ketal Chemicals India Pvt Ltd
Priority to PL12839189T priority Critical patent/PL2785780T3/en
Publication of EP2785780A1 publication Critical patent/EP2785780A1/en
Application granted granted Critical
Publication of EP2785780B1 publication Critical patent/EP2785780B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

  • the present invention relates to amine and nitroxide based additive composition for control and inhibition of polymerization of aromatic vinyl monomers, ⁇ wherein aromatic vinyl monomer include styrene.
  • the present invention relates to use of amine and nitroxide based additive composition of present invention to control and inhibit polymerization of aromatic vinyl monomers including styrene.
  • the present invention relates to method of preparation of amine and nitroxide based additive composition of present invention for control and inhibition of polymerization of aromatic vinyl monomers including styrene.
  • the present invention relates to method of controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing amine and nitroxide based additive composition of present invention.
  • the problem of using the inhibitors alone is that these are to be added continuously or at regular interval, because once they are consumed, the polymerization will re-start.
  • the problem of using the retarders alone is that these are not very effective to reduce polymerization of styrene to a level of substantial inhibition or to the acceptable level of inhibition.
  • the US '760 discloses and teaches use of combination of nitroxides (i.e. nitroxyl) compound and aromatic nitro compound.
  • the US'760 discloses and teaches against the use of either of nitroxides (i.e. nitroxyl) compound or of aromatic nitro compound [Re Col. 5, lines 50-56; Col. 6, lines 10-14 and 42-46; Col. 7, lines 36-41 of US'760].
  • aromatic nitro compounds including DNBP are to be used in higher amounts and/or are also known for their toxic nature for human exposure [re Col. 1, lines 64-68 of US'760].
  • the present invention aims at providing a solution to above-described existing industrial problems by providing effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also does not comprise aromatic nitro compounds.
  • the present invention also aims at providing an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
  • the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
  • the main object of present invention is to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also does not comprise aromatic nitro compounds.
  • Another main object of present invention is to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
  • the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
  • nitroxides i.e. nitroxyl
  • the amine is aliphatic amine.
  • the present invention particularly aims at providing an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition comprises one or more of amines and reduced or minimized amount of one or more of nitroxides (i.e. nitroxyl) compounds, and does not comprise aromatic nitro compounds, and is still suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, and is still required in relatively lower dosage as compared to dosage of nitroxides (i.e.
  • nitroxyl compounds alone for achieving the same or better acceptable level of control and inhibition of polymerization of aromatic vinyl monomers including styrene, and wherein the amine is aliphatic amine, which is selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine, and therefore, the composition of present invention is not only economical, but is also environment friendly.
  • the present invention also aims at improving the performance of nitroxide (i.e. nitroxyl) compounds at a wider range of temperature including the higher temperature and in presence of air, wherein the composition further comprises one or more aliphatic amines.
  • nitroxide i.e. nitroxyl
  • composition consisting of nitroxide i.e. nitroxyl
  • nitroxide i.e. nitroxyl
  • polymerization of aromatic vinyl monomers including styrene surprisingly and unexpectedly, is also controlled and inhibited to the acceptable lever at substantially reduced dosages of composition comprising one or more of nitroxide compounds and one or more of aliphatic amine compounds, which makes the composition economical as well as environment friendly.
  • the inventor has found that when one or more of aliphatic tertiary amines, or aliphatic tertiary amines containing one or more hydroxyl groups or one or more of secondary amines or one or more of primary amines or mixture thereof is added to composition consisting of one or more of nitroxide (i.e.
  • nitroxyl nitroxyl compounds without aromatic nitro compounds
  • polymerization of aromatic vinyl monomers including styrene surprisingly and unexpectedly, is also controlled and inhibited to the acceptable level at substantially reduced dosages of composition comprising nitroxide and aliphatic amine compounds, which makes the composition economical as well as environment friendly.
  • the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
  • aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine.
  • the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
  • the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
  • the aliphatic amine is an aliphatic tertiary amine, which contains one or more hydroxyl groups in the alkyl chain of the tertiary amine, preferably it contains three hydroxyl groups in the alkyl chain of the tertiary amine, more preferably the hydroxyl groups are hydroxyalkyl groups.
  • the said amine is hydroxyl alkyl tertiary amine.
  • the said amine is ethylene oxide treated amine.
  • the said amine is propylene oxide treated amine.
  • the said amine is tertiary alkyl amine.
  • the said amine is mixture of one or more of hydroxyl alkyl tertiary amines, ethylene oxide treated amines, propylene oxide treated amines, tertiary alkyl amines.
  • the said hydroxyl alkyl tertiary amine is tris(2-hydroxypropyl)amine (TIP A).
  • the said ethylene oxide treated amine is ⁇ , ⁇ , ⁇ ' , ⁇ '-Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED).
  • the said propylene oxide treated amine is ⁇ , ⁇ , ⁇ ', ⁇ '-Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol).
  • the said hydroxyl alkyl tertiary amine is triethanolamine (TEA).
  • the said tertiary alkyl amine is TrisfN-butylamine] (TBA).
  • the said primary amine is selected from a group comprising hydroxyl alkyl primary amine and alkyl primary amine.
  • the said secondary amine is alkyl secondary amine.
  • the said hydroxyl alkyl primary amine is monoethanolamine (MEA).
  • the said alkyl primary amine is octyl amine (OA).
  • the said alkyl secondary amine is dibutyl amine (DBA).
  • composition of present invention comprises one or more of said amines
  • efficiency of nitroxide compounds to control and inhibit polymerization of aromatic vinyl monomers including styrene is, surprisingly and unexpectedly, substantially improved to the acceptable level that's too at substantially reduced dosages of nitroxide compounds and that's too without aromatic nitro compounds, thereby making the composition of present invention relatively more economical and environment friendly.
  • composition of present invention comprises:
  • the composition of present invention is added to the stream containing aromatic vinyl monomers including styrene in an amount varying from about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm by weight of the stream of monomer including styrene.
  • the nitroxide (or nitroxyl) compound is selected from the group comprising di-tert-butylnitroxyl, l-oxyl-2,2,6,6- tetramethylpiperidine, l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl -2,2,6,6- tetramefhylpiperidin-4-one, and derivatives thereof; and di-nitroxides and derivatives comprising bis(l -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(l -oxyl-2,2,6,6- tetramethylpiperidin-4-yl)succinate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4- yl)adipate, and mixture thereof.
  • nitroxyl compound is selected from the group comprising bis(l -oxyl-2,2,6,6- tetramethylpiperidin-4-yl)sebacate and 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol or 4- hydroxy-2,2,6,6-tetramethylpiperidin- 1-oxyl (or 4 Hydroxy Tempo or 4-HT), and mixture thereof.
  • the nitroxide (or nitroxyl) compound is 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol (or 4 Hydroxy Tempo or 4-HT).
  • the present composition does not comprise aromatic nitro compound.
  • the present invention also relates to method of using amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, to control and inhibit polymerization of aromatic vinyl monomers including styrene, wherein the stream comprising aromatic vinyl monomer including styrene is treated with an additive composition comprising one or more of nitroxides (i.e. nitro xyls) compounds and one or more of said amines.
  • nitroxides i.e. nitro xyls
  • the present invention relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises:
  • aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine;
  • said monomers are treated with said composition.
  • the present invention particularly relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises:
  • said monomers are treated with said composition.
  • the present invention also relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises: (a) one or more of nitroxides (i.e. nitroxyls) compounds; and ⁇ characterized in that the said composition further comprises one or more of
  • amines selected from a group consisting of primary amines and secondary amines
  • said monomers are treated with said composition.
  • stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
  • the method of using said additive composition of the present invention comprises treating said monomers stream with about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm of said composition based on weight of monomers.
  • composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method of using said additive composition of the present invention.
  • the present invention also relates to method for controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, wherein the stream comprising aromatic vinyl monomers including styrene is treated with an additive composition comprising one or more of nitroxides (i.e. nitroxyls) compounds and one or more of said amines.
  • nitroxides i.e. nitroxyls
  • the present invention relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
  • aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine;
  • composition is added to said monomers.
  • the present invention particularly relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
  • composition is added to said monomers.
  • the present invention also relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
  • amines selected from a group consisting of primary amines and secondary amines
  • composition is added to said monomers.
  • stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
  • the method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing said additive composition of the present invention comprises adding from about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm of said composition to the aromatic vinyl monomers stream including styrene based on weight of monomers.
  • composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing said additive composition of the present invention.
  • the composition of present invention may be mixed with or added to the monomers stream containing aromatic vinyl monomers including styrene either before the stream enters into processing system or after the stream has entered into processing system, but preferably the composition is added to the stream containing aromatic vinyl monomers before its processing starts so that polymerization of aromatic vinyl monomers is avoided.
  • the nitroxide compounds and the amine compounds may be mixed with or added to the monomers stream individually or after mixing.
  • the present composition may be used in or employed with or added to monomers stream over a wide range of temperature varying from about 50 degree C to about 180 degree C, preferably from about 60 degree C to about 180 degree C.
  • composition of present invention may be prepared in any known manner to prepare the compositions.
  • the present invention also relates to method of preparing amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, for controlling and inhibiting polymerization of aromatic vinyl monomers including styrene, wherein the nitroxide and said amine compounds are added individually or after mixing.
  • the present invention relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
  • the present invention particularly relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
  • the present invention also relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
  • (B) amines selected from a group consisting of primary amines and secondary amines.
  • stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
  • composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method for preparation of additive composition of the present invention.
  • the inventor has found that when present composition comprises any one of the amines selected from a group consisting of ⁇ , ⁇ , ⁇ ', ⁇ '-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and ⁇ , ⁇ , ⁇ ', ⁇ ' - Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is substantially improved, however, the efficiency improvement is riot as substantial as for the composition comprising tris(2-hydroxypropyl)amine (TIPA). Therefore, as per most preferred embodiment of the present invention, tris(2- hydroxypropyl)amine (TIPA) is most preferred amine.
  • TIPA tris(2- hydroxypropyl)amine
  • the inventor has found that-when present composition comprises any one of the amines selected from a group consisting of triethanolamine (TEA), Tris[N-butylamine] (TBA), monoethanolamine (MEA), octyl amine (OA), dibutyl amine (DBA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is improved, however, the efficiency improvement is not as substantial as for the composition comprising ⁇ , ⁇ , ⁇ ', ⁇ '-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) or ⁇ , ⁇ , ⁇ ' , ⁇ ' - Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol).
  • TAEED triethanolamine
  • QED dibutyl amine
  • ⁇ , ⁇ , ⁇ ' , ⁇ ' -Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and ⁇ , ⁇ , ⁇ ' , ⁇ ' -Tetrakis (2-hydroxypropyl) ethylene- diamine) (Quadrol) are the more preferred amines. It has been found that dibutyl amine (DBA), surprisingly and unexpectedly, demonstrates better efficiency when used in compositions of dosages of about 200 ppm or more.
  • DBA dibutyl amine
  • composition comprises any one of the amines selected from a group consisting of N,N,disec-butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is not improved.
  • UOP5 N,N,disec-butyl-para-phenylene diamine
  • EDA ethylene diamine
  • TEPA tetraethylenepentamine
  • DP A dipropyl amine
  • DEA diethanol amine
  • the present composition does not comprise any one of the amines selected from a group consisting of N,N,disec-butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA). It may be noted that some of these amines result in very marginal improvement in efficiency of nitroxides, but same is not commercially viable.
  • UOP5 N,N,disec-butyl-para-phenylene diamine
  • EDA ethylene diamine
  • TEPA tetraethylenepentamine
  • DP A dipropyl amine
  • DEA diethanol amine
  • styrene was purified before use to remove the stabilizers.
  • the prior additive is a nitroxide, which is 1 oxyl-2,2,6,6, tetrarnethylpiepridin-4-ol (or 4 Hydroxy Tempo or 4-HT), which was taken in an amount of about 100, 200, 300, 500, or 1000 ppm by weight of styrene.
  • the present additive is a composition comprising nitroxide which is l-oxyl-2,2,6,6, tetramethylpiepridin-4-ol (4 Hydroxy Tempo or 4- HT), and aliphatic tertiary amine, which is tri-isopropanol amine (TIP A) containing three hydroxyl groups, wherein from about 1 to about 20 ppm of TIPA is added to the weighed amount of nitroxide.
  • nitroxide which is l-oxyl-2,2,6,6, tetramethylpiepridin-4-ol (4 Hydroxy Tempo or 4- HT)
  • TIP A tri-isopropanol amine
  • the %polymer formed with 100 ppm of 4-HT alone is substantially reduced from 13.19% to 1 1.22%, to 10.9%, to 6.28%, and to 4.3%, respectively when 4 ppm (3.85% of total composition), 10 ppm (9.09% of total composition), 15 ppm (13.04% of total composition) and 20 ppm (16.67% of total composition) of TIP A is added to 100 ppm of 4HT.
  • the %polymer formed is, surprisingly and unexpectedly, substantially less than %polymer formed with composition consisting of 200 ppm of 4-HT, meaning thereby, the present composition results in saving of half of dosage of 4-HT, and hence is economical and environment friendly.
  • the %polymer formed is, surprisingly and unexpectedly, substantially less than %polymer formed with composition consisting of 300 ppm of 4-HT, meaning thereby, the present composition results in saving of two-third of dosage of 4-HT, and hence, is economical and environment friendly.
  • the %polymer formed with 500 ppm of 4-HT alone is substantially reduced even at higher temperature of about 135°C from 16.7% to 6.45%, to 6.05%, to 5.72%, and to 4.9%, respectively when 5 ppm Gust 0.99% of total composition), 10 ppm (just 1.96% of total composition), 15 ppm (just 2.91% of total composition) and 20 ppm (just 3.85% of total composition) of TIPA is added to 500 ppm of 4HT. The reduction achieved is even greater than about 3 times.
  • the %polymer formed is, surprisingly and unexpectedly, less than %polymer formed with composition consisting of 1000 ppm of 4-HT, meaning thereby, the present composition results in saving of half of dosage of 4-HT, and hence is economical and environment friendly.
  • the prior art additive composition is 4HT, which is taken in an amount of about 100, 200, and 300 ppm
  • the present additive composition is a composition comprising 4HT being nitroxide, and additionally comprising TIPA, THEED, Quadrol, TEA, TBA, MEA, OA, DBA being amines of the present invention, which are taken in weight ratio of 99:1, 98:2, 95:5, 90: 10, 85: 15, 80:20, 70:30 and 50:50, the composition is made to 100, 200 and 300 ppm.
  • the inventor has further compared the results of present compositions with additive compositions comprising 4HT and amine selected from a group consisting of UOP5, EDA, TEPA, DP A, or DEA for comparative purposes.
  • composition comprises any one of the amines selected from a group consisting of ⁇ , ⁇ , ⁇ ', ⁇ ' -Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED) and ⁇ , ⁇ , ⁇ ' , ⁇ ' -Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is substantially improved, however, the improvement is not as substantial as for the composition comprising tris(2- hydroxypropyl)amine (TIPA). Therefore, as per most preferred embodiment of the present invention, tris(2-hydroxypropyl)amine (TIPA) is most preferred amine.
  • TIPA tris(2-hydroxypropyl)amine
  • composition comprises any one of the amines selected from a group consisting of triethanolamine (TEA), Tris[N-butylamine] (TBA), monoethanolamine (MEA), octyl amine (OA), dibutyl amine (DBA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is improved, however, the improvement is not as substantial as for the composition comprising ⁇ , ⁇ , ⁇ ' , ⁇ ' -Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED) or ⁇ , ⁇ , ⁇ ', ⁇ ' -Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol).
  • ⁇ , ⁇ , ⁇ ', ⁇ '-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and ⁇ , ⁇ , ⁇ ', ⁇ '- Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol) are the more preferred amines.
  • dibutyl amine surprisingly and unexpectedly, demonstrates better efficiency when used in compositions of dosages of about 200 ppm or more.
  • the composition comprises any one of the comparative amines selected from a group consisting of N,N,disec-butyl-para- phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is not improved.
  • UOP5 N,N,disec-butyl-para- phenylene diamine
  • EDA ethylene diamine
  • TEPA tetraethylenepentamine
  • DP A dipropyl amine
  • DEA diethanol amine
  • the present composition does not comprise any one of the amines selected from a group consisting of N,N,disec- butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA). It may be noted that some of these amines result in very marginal improvement in efficiency of nitroxides, but same is not commercially viable.
  • UOP5 N,N,disec- butyl-para-phenylene diamine
  • EDA ethylene diamine
  • TEPA tetraethylenepentamine
  • DP A dipropyl amine
  • DEA diethanol amine
  • composition is far superior than prior art additive, and hence, has technical advantages and surprising effects over the prior art additive. It may be noted that the term "about” as employed herein is not intended to enlarge scope of claimed invention, but has been incorporated only to include experimental errors permissible in the field of the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

The present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising: (a) one or more of nitroxide (i.e. nitroxyl) compounds; and characterized in that the said composition further comprises one or more of (b) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines. In one embodiment, the present invention also relates to method of use of presently provided composition. In another embodiment, the present invention also relates to method of controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing presently provided composition. In still another embodiment, the present invention also relates to method of preparation of presently provided composition.

Description

Title of the invention:
Amine and Nitroxide based Additive Composition for control and inhibition of polymerization of styrene, and method of use thereof. Field of the invention:
The present invention relates to amine and nitroxide based additive composition for control and inhibition of polymerization of aromatic vinyl monomers, · wherein aromatic vinyl monomer include styrene.
In one embodiment, the present invention relates to use of amine and nitroxide based additive composition of present invention to control and inhibit polymerization of aromatic vinyl monomers including styrene.
In another embodiment, the present invention relates to method of preparation of amine and nitroxide based additive composition of present invention for control and inhibition of polymerization of aromatic vinyl monomers including styrene.
In still another embodiment, the present invention relates to method of controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing amine and nitroxide based additive composition of present invention. Background of the invention:
The polymerization of aromatic vinyl monomers including styrene during processing is a matter of concern, because it causes formation of unwanted polymers and results in loss of yield of end product and makes the process un-economical.
In the art use of inhibitors and retarders, and combination thereof to overcome problem of polymerization of styrene has been reported.
The problem of using the inhibitors alone is that these are to be added continuously or at regular interval, because once they are consumed, the polymerization will re-start.
The problem of using the retarders alone is that these are not very effective to reduce polymerization of styrene to a level of substantial inhibition or to the acceptable level of inhibition.
The prior art [US 5,254,760 (US '760)] discloses the polymerization inhibition of vinyl monomers using a combination of nitroxides (i.e. nitroxyl compounds) including 1 oxyl -2,2,6,6, tetramethylpiepridin-4-ol (4HT) and aromatic nitro compounds including dinitro-butylphenol [re abstract, Col. 3, lines 26-32; Col. 4, lines 1-2, 12 of US 760] as the polymerization inhibitor.
The US '760 discloses and teaches use of combination of nitroxides (i.e. nitroxyl) compound and aromatic nitro compound. The US'760 discloses and teaches against the use of either of nitroxides (i.e. nitroxyl) compound or of aromatic nitro compound [Re Col. 5, lines 50-56; Col. 6, lines 10-14 and 42-46; Col. 7, lines 36-41 of US'760].
However, the aromatic nitro compounds including DNBP are to be used in higher amounts and/or are also known for their toxic nature for human exposure [re Col. 1, lines 64-68 of US'760].
Therefore, the industry is aiming for additive composition wherein the aromatic nitro compounds can be avoided. Any effort to avoid consumption of aromatic nitro compounds will lessen the problem of industry. Need of the Invention:
Therefore, there is still a need of an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers by employing said composition, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also does not comprise aromatic nitro compounds.
Problem to be solved by the Invention:
Therefore, the present invention aims at providing a solution to above-described existing industrial problems by providing effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also does not comprise aromatic nitro compounds.
In-addition to above aim, the present invention also aims at providing an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
Objects of the Invention:
Accordingly, the main object of present invention is to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also does not comprise aromatic nitro compounds.
Another main object of present invention is to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, but also comprises reduced or minimized amount of nitroxides (i.e. nitroxyl) compounds.
This is also an object of present invention to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition comprises reduced or minimized amount of one or more of nitroxides (i.e. nitroxyl) compounds, and does not comprise aromatic nitro compounds, and is still suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, and is still required in relatively lower dosage as compared to dosage of nitroxides (i.e. nitroxyl) compounds alone for achieving the same or better acceptable level of control and inhibition of polymerization of aromatic vinyl monomers including styrene.
This is also an object of present invention to provide an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the . additive composition comprises one or more of amines and reduced or minimized amount of one or more of nitroxides (i.e. nitroxyl) compounds, and does not comprise aromatic nitro compounds, and is still suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, and is still required in relatively lower dosage as compared to dosage of nitroxides (i.e. nitroxyl) compounds alone for achieving the same or better acceptable level of control and inhibition of polymerization of aromatic vinyl monomers including styrene, and wherein the amine is aliphatic amine.
The present invention particularly aims at providing an effective additive composition and method of its use and preparation, and method of controlling and inhibiting polymerization of vinyl aromatic monomers, wherein the additive composition comprises one or more of amines and reduced or minimized amount of one or more of nitroxides (i.e. nitroxyl) compounds, and does not comprise aromatic nitro compounds, and is still suitable for substantial control and inhibition of polymerization of aromatic vinyl monomers including styrene, and is still required in relatively lower dosage as compared to dosage of nitroxides (i.e. nitroxyl) compounds alone for achieving the same or better acceptable level of control and inhibition of polymerization of aromatic vinyl monomers including styrene, and wherein the amine is aliphatic amine, which is selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine, and therefore, the composition of present invention is not only economical, but is also environment friendly.
The present invention also aims at improving the performance of nitroxide (i.e. nitroxyl) compounds at a wider range of temperature including the higher temperature and in presence of air, wherein the composition further comprises one or more aliphatic amines.
Other objects and advantages of present invention will become more apparent from the following description when read in conjunction with examples, which are not intended to limit scope of present invention.
Description and Preferred Embodiments of the Invention:
With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has found that when an aliphatic amine is added to composition consisting of nitroxide (i.e. nitroxyl) compounds even without aromatic nitro compounds, then not only polymerization controlling and inhibiting efficiency of nitroxides is substantially improved, but polymerization of aromatic vinyl monomers including styrene, surprisingly and unexpectedly, is also controlled and inhibited to the acceptable lever at substantially reduced dosages of composition comprising one or more of nitroxide compounds and one or more of aliphatic amine compounds, which makes the composition economical as well as environment friendly.
With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has found that when one or more of aliphatic tertiary amines, or aliphatic tertiary amines containing one or more hydroxyl groups or one or more of secondary amines or one or more of primary amines or mixture thereof is added to composition consisting of one or more of nitroxide (i.e. nitroxyl) compounds without aromatic nitro compounds, then not only polymerization controlling and inhibiting efficiency of nitroxides is substantially improved, but polymerization of aromatic vinyl monomers including styrene, surprisingly and unexpectedly, is also controlled and inhibited to the acceptable level at substantially reduced dosages of composition comprising nitroxide and aliphatic amine compounds, which makes the composition economical as well as environment friendly.
Accordingly, the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine.
Accordingly, in one embodiment, the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) tertiary amines.
Accordingly, in another embodiment, the present invention relates to additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) amines selected from a group consisting of primary amines and secondary amines. In accordance with present invention, the aliphatic amine is an aliphatic tertiary amine, which contains one or more hydroxyl groups in the alkyl chain of the tertiary amine, preferably it contains three hydroxyl groups in the alkyl chain of the tertiary amine, more preferably the hydroxyl groups are hydroxyalkyl groups.
In accordance with one of the most preferred embodiments of the present invention, the said amine is hydroxyl alkyl tertiary amine.
In accordance with one of the preferred embodiments of the present invention, the said amine is ethylene oxide treated amine.
In accordance with one of the preferred embodiments of the present invention, the said amine is propylene oxide treated amine.
In accordance with one of the preferred embodiments of the present invention, the said amine is tertiary alkyl amine.
In accordance with one of the preferred embodiments of the present invention, the said amine is mixture of one or more of hydroxyl alkyl tertiary amines, ethylene oxide treated amines, propylene oxide treated amines, tertiary alkyl amines.
In accordance with one of the most preferred embodiments of the present invention, the said hydroxyl alkyl tertiary amine is tris(2-hydroxypropyl)amine (TIP A).
In accordance with one of the preferred embodiments of the present invention, the said ethylene oxide treated amine is Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED).
In accordance with one of the preferred embodiments of the present invention, the said propylene oxide treated amine is Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol).
In accordance with one of the preferred embodiments of the present invention, the said hydroxyl alkyl tertiary amine is triethanolamine (TEA).
In accordance with one of the preferred embodiments of the present invention, the said tertiary alkyl amine is TrisfN-butylamine] (TBA).
In accordance with one of the embodiments of the present invention, the said primary amine is selected from a group comprising hydroxyl alkyl primary amine and alkyl primary amine.
In accordance with one of the embodiments of the present invention, the said secondary amine is alkyl secondary amine.
In accordance with one of the embodiments of the present invention, the said hydroxyl alkyl primary amine is monoethanolamine (MEA). In accordance with one of the embodiments of the present invention, the said alkyl primary amine is octyl amine (OA).
In accordance with one of the embodiments of the present invention, the said alkyl secondary amine is dibutyl amine (DBA).
It has been found that when composition of present invention comprises one or more of said amines, the efficiency of nitroxide compounds to control and inhibit polymerization of aromatic vinyl monomers including styrene is, surprisingly and unexpectedly, substantially improved to the acceptable level that's too at substantially reduced dosages of nitroxide compounds and that's too without aromatic nitro compounds, thereby making the composition of present invention relatively more economical and environment friendly.
In accordance with one of the embodiments of the present invention, the composition of present invention comprises:
a) about 40 to about 99.75 % by weight of 1) said nitroxide (i.e. nitroxyl) compounds; and
b) about 0.25 to about 60 % by weight of II) said amines or mixture thereof.
In accordance with one of the preferred embodiments of the present invention, the composition of present invention is added to the stream containing aromatic vinyl monomers including styrene in an amount varying from about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm by weight of the stream of monomer including styrene.
In accordance with present invention, the nitroxide (or nitroxyl) compound is selected from the group comprising di-tert-butylnitroxyl, l-oxyl-2,2,6,6- tetramethylpiperidine, l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl -2,2,6,6- tetramefhylpiperidin-4-one, and derivatives thereof; and di-nitroxides and derivatives comprising bis(l -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(l -oxyl-2,2,6,6- tetramethylpiperidin-4-yl)succinate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4- yl)adipate, and mixture thereof.
In accordance with preferred embodiment of the present invention, the nitroxide
(or nitroxyl) compound is selected from the group comprising bis(l -oxyl-2,2,6,6- tetramethylpiperidin-4-yl)sebacate and 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol or 4- hydroxy-2,2,6,6-tetramethylpiperidin- 1-oxyl (or 4 Hydroxy Tempo or 4-HT), and mixture thereof. In accordance with most preferred embodiment <of the present invention, the nitroxide (or nitroxyl) compound is 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol (or 4 Hydroxy Tempo or 4-HT).
In accordance with one of the preferred embodiments of the present invention, the present composition does not comprise aromatic nitro compound.
Accordingly, in another embodiment, the present invention also relates to method of using amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, to control and inhibit polymerization of aromatic vinyl monomers including styrene, wherein the stream comprising aromatic vinyl monomer including styrene is treated with an additive composition comprising one or more of nitroxides (i.e. nitro xyls) compounds and one or more of said amines.
In particular, in second embodiment, the present invention relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine; and
said monomers are treated with said composition.
Accordingly, in this second embodiment, the present invention particularly relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) tertiary amines; and
said monomers are treated with said composition.
Accordingly, in this second embodiment, the present invention also relates to a method of using additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises: (a) one or more of nitroxides (i.e. nitroxyls) compounds; and · characterized in that the said composition further comprises one or more of
(b) amines selected from a group consisting of primary amines and secondary amines; and
said monomers are treated with said composition.
It may be noted that the stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
In accordance with one of the embodiments of the present invention, the method of using said additive composition of the present invention comprises treating said monomers stream with about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm of said composition based on weight of monomers.
It may be noted that all the features of the composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method of using said additive composition of the present invention.
Accordingly, in third embodiment, the present invention also relates to method for controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, wherein the stream comprising aromatic vinyl monomers including styrene is treated with an additive composition comprising one or more of nitroxides (i.e. nitroxyls) compounds and one or more of said amines.
In particular, in third embodiment, the present invention relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the amine is tertiary amine; and
said composition is added to said monomers.
Accordingly, in this third embodiment, the present invention particularly relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) tertiary amines; and
said composition is added to said monomers.
Accordingly, in this third embodiment, the present invention also relates to a method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing additive composition of the present invention described herein, a reference to which is drawn in entirety, wherein said composition comprises:
(a) one or more of nitroxides (i.e. nitroxyls) compounds; and
characterized in that the said composition further comprises one or more of
(b) amines selected from a group consisting of primary amines and secondary amines; and
said composition is added to said monomers.
It may be noted that the stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
In accordance with one of the embodiments of the present invention, the method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing said additive composition of the present invention comprises adding from about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm of said composition to the aromatic vinyl monomers stream including styrene based on weight of monomers.
It may be noted that all the features of the composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by employing said additive composition of the present invention.
In accordance with one of the embodiments of the present invention, the composition of present invention may be mixed with or added to the monomers stream containing aromatic vinyl monomers including styrene either before the stream enters into processing system or after the stream has entered into processing system, but preferably the composition is added to the stream containing aromatic vinyl monomers before its processing starts so that polymerization of aromatic vinyl monomers is avoided.
In accordance with one of the embodiments of the present invention, the nitroxide compounds and the amine compounds may be mixed with or added to the monomers stream individually or after mixing.
In accordance with one of the embodiments of the present invention, the present composition may be used in or employed with or added to monomers stream over a wide range of temperature varying from about 50 degree C to about 180 degree C, preferably from about 60 degree C to about 180 degree C.
The composition of present invention may be prepared in any known manner to prepare the compositions.
Accordingly, in fourth embodiment, the present invention also relates to method of preparing amine and nitroxide based additive composition of present invention described herein, a reference to which is drawn in entirety, for controlling and inhibiting polymerization of aromatic vinyl monomers including styrene, wherein the nitroxide and said amine compounds are added individually or after mixing.
In particular, in fourth embodiment, the present invention relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
(A) mixing one or more of said nitroxide (i.e. nitroxyl) compounds,
characterized in that said nitroxide compound or mixture thereof is further mixed with one or more of
(B) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines, preferably the tertiary amines.
Accordingly, in this fourth embodiment, the present invention particularly relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
(A) mixing one or more of said nitroxide (i.e. nitroxyl) compounds,
characterized in that said nitroxide compound or mixture thereof is further mixed with one or more of
(B) tertiary amines. Accordingly, in this fourth embodiment, the present invention also relates to a method for preparation of additive composition of the present invention described herein, a reference to which is drawn in entirety, for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein the method comprises:
(A) mixing one or more of said nitroxide (i.e. nitroxyl) compounds,
characterized in that said nitroxide compound or mixture thereof is further mixed with one or more of
(B) amines selected from a group consisting of primary amines and secondary amines.
It may be noted that the stream comprising aromatic vinyl monomers including styrene may be referred to as stream or monomers stream or as aromatic vinyl monomers stream.
It may be noted that all the features of the composition of the present invention described herein, a reference to which is drawn in entirety, are deemed to have been included in present method for preparation of additive composition of the present invention.
In one of the embodiments, the inventor has found that when present composition comprises any one of the amines selected from a group consisting of Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and Ν,Ν,Ν',Ν'- Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is substantially improved, however, the efficiency improvement is riot as substantial as for the composition comprising tris(2-hydroxypropyl)amine (TIPA). Therefore, as per most preferred embodiment of the present invention, tris(2- hydroxypropyl)amine (TIPA) is most preferred amine.
In another embodiment, the inventor has found that-when present composition comprises any one of the amines selected from a group consisting of triethanolamine (TEA), Tris[N-butylamine] (TBA), monoethanolamine (MEA), octyl amine (OA), dibutyl amine (DBA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is improved, however, the efficiency improvement is not as substantial as for the composition comprising Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) or Ν,Ν,Ν',Ν'- Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol). Therefore, as per more preferred embodiment of the present invention, Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxypropyl) ethylene- diamine) (Quadrol) are the more preferred amines. It has been found that dibutyl amine (DBA), surprisingly and unexpectedly, demonstrates better efficiency when used in compositions of dosages of about 200 ppm or more.
In still another embodiment, the inventor has found that when present composition comprises any one of the amines selected from a group consisting of N,N,disec-butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is not improved. Therefore, in one embodiment, the present composition does not comprise any one of the amines selected from a group consisting of N,N,disec-butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA). It may be noted that some of these amines result in very marginal improvement in efficiency of nitroxides, but same is not commercially viable.
Further advantages and embodiments of the present invention will become more apparent from the following examples.
The present invention is now described with the help of following examples, which are not intended to limit scope of the present invention, but have been incorporated to illustrate mode and best mode of performing the present invention.
Experiments:
Main Experiment:
In the following experiments, weighed amount of distilled styrene and additives were taken in a reactor (tube reactor or round bottom reactor) equipped with thermometer and nitrogen inlet and outlet. In these experiments a tube reactor was used without any mechanical stirrer, and enough N2 flow was maintained to ensure proper agitation. The reactions were carried out at about 120°C for about 2 hours. After the selected duration, the reactor was cooled to below about 10°C by immersing in crushed ice. The contents of the reactor were then poured in a beaker. To this same beaker, approximately for 1.5-2g chilled polymerization mixture, about 80g methanol was used to precipitate the polymer formed in the styrene solution. The precipitate obtained was filtered, dried to remove methanol, and weighed. The weight of the precipitate was reported as % polymer formed in following tables.
It may be noted that styrene was purified before use to remove the stabilizers. In following examples, the prior additive is a nitroxide, which is 1 oxyl-2,2,6,6, tetrarnethylpiepridin-4-ol (or 4 Hydroxy Tempo or 4-HT), which was taken in an amount of about 100, 200, 300, 500, or 1000 ppm by weight of styrene.
In the following examples, the present additive is a composition comprising nitroxide which is l-oxyl-2,2,6,6, tetramethylpiepridin-4-ol (4 Hydroxy Tempo or 4- HT), and aliphatic tertiary amine, which is tri-isopropanol amine (TIP A) containing three hydroxyl groups, wherein from about 1 to about 20 ppm of TIPA is added to the weighed amount of nitroxide.
Experiment 1 -
The results of above Main Experiment when performed with lOg of distilled styrene by heating to 120°C for 2h are provided in Table 1.
Table-I
It is understood from above Table-I that when just 4 ppm to 20 ppm of TIP A is added to 100 ppm of 4HT (prior art additive), the efficiency of 4-HT to control and inhibit polymerization of styrene is, surprisingly and unexpectedly, improved substantially.
It can also be seen from Table-I that polymerization of styrene is, surprisingly and unexpectedly, substantially reduced just on addition of 4 to 20 ppm of TIP A in 100 ppm of 4HT (prior art additive).
It may be noted, the %polymer formed with 100 ppm of 4-HT alone is substantially reduced from 13.19% to 1 1.22%, to 10.9%, to 6.28%, and to 4.3%, respectively when 4 ppm (3.85% of total composition), 10 ppm (9.09% of total composition), 15 ppm (13.04% of total composition) and 20 ppm (16.67% of total composition) of TIP A is added to 100 ppm of 4HT.
It can also be seen from Table-I that for composition comprising 100 ppm of 4HT and 15 ppm of TIPA (13.04% of TIPA of total composition), the %polymer formed is, surprisingly and unexpectedly, substantially less than %polymer formed with composition consisting of 200 ppm of 4-HT, meaning thereby, the present composition results in saving of half of dosage of 4-HT, and hence is economical and environment friendly.
It can also be seen from Table-I that for composition comprising 100 ppm of 4HT and 20 ppm of TIPA (16.67% of TIPA of total composition), the %polymer formed is, surprisingly and unexpectedly, substantially less than %polymer formed with composition consisting of 300 ppm of 4-HT, meaning thereby, the present composition results in saving of two-third of dosage of 4-HT, and hence, is economical and environment friendly.
Experiment 2 -
The results of above Main Experiment when performed with lOg of distilled styrene by heating to 135°C for 2h are provided in Table-II. Table-II
It is understood from above Table-II that when just 5 ppm to 20 ppm of TIPA is added even to higher dosage of 500 ppm of 4HT (prior art additive) and styrene stream with additive is treated even at higher temperature of 135°C, the efficiency of 4-HT to control and inhibit polymerization of styrene is, surprisingly and unexpectedly, improved substantially.
It can also be seen from Table-II that polymerization of styrene is, surprisingly and unexpectedly, substantially reduced just on addition of 5 to 20 ppm of TIPA in 500 ppm of 4HT (prior art additive).
It may be noted the %polymer formed with 500 ppm of 4-HT alone is substantially reduced even at higher temperature of about 135°C from 16.7% to 6.45%, to 6.05%, to 5.72%, and to 4.9%, respectively when 5 ppm Gust 0.99% of total composition), 10 ppm (just 1.96% of total composition), 15 ppm (just 2.91% of total composition) and 20 ppm (just 3.85% of total composition) of TIPA is added to 500 ppm of 4HT. The reduction achieved is even greater than about 3 times.
It can also be seen from Table-II that for composition comprising 500 ppm of 4HT and 10 ppm of TIPA Gust 1.96% of TIPA of total composition), the %polymer formed is, surprisingly and unexpectedly, less than %polymer formed with composition consisting of 1000 ppm of 4-HT, meaning thereby, the present composition results in saving of half of dosage of 4-HT, and hence is economical and environment friendly.
Experiments 3 to 5:
In following examples, for above Main Experiment, the prior art additive composition is 4HT, which is taken in an amount of about 100, 200, and 300 ppm, and the present additive composition is a composition comprising 4HT being nitroxide, and additionally comprising TIPA, THEED, Quadrol, TEA, TBA, MEA, OA, DBA being amines of the present invention, which are taken in weight ratio of 99:1, 98:2, 95:5, 90: 10, 85: 15, 80:20, 70:30 and 50:50, the composition is made to 100, 200 and 300 ppm.
The inventor has further compared the results of present compositions with additive compositions comprising 4HT and amine selected from a group consisting of UOP5, EDA, TEPA, DP A, or DEA for comparative purposes.
As can be seen from data in Tables III, IV and V, with addition of about 1 to about 150 ppm of TIPA, THEED, Quadrol, TEA, TBA, MEA, OA or DBA to 4HT making total of 100, 200 and 300 ppm of the composition so as to have 4HT : Amine in a weight ratio of 99:1, 98:2, 95:5, 90:10, 85:15, 80:20, 70:30 and 50:50, the efficiency of prior art additive composition consisting of 4HT to control and inhibit polymerization of styrene is, surprisingly and unexpectedly, generally improved.
As can be seen, when present composition comprises any one of the amines selected from a group consisting of Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED) and Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is substantially improved, however, the improvement is not as substantial as for the composition comprising tris(2- hydroxypropyl)amine (TIPA). Therefore, as per most preferred embodiment of the present invention, tris(2-hydroxypropyl)amine (TIPA) is most preferred amine.
As can also be seen, when present composition comprises any one of the amines selected from a group consisting of triethanolamine (TEA), Tris[N-butylamine] (TBA), monoethanolamine (MEA), octyl amine (OA), dibutyl amine (DBA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is improved, however, the improvement is not as substantial as for the composition comprising Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED) or Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol). Therefore, as per more preferred embodiment of the present invention, Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene-diamine) (THEED) and Ν,Ν,Ν',Ν'- Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol) are the more preferred amines.
As can be seen, dibutyl amine (DBA), surprisingly and unexpectedly, demonstrates better efficiency when used in compositions of dosages of about 200 ppm or more.
As can also been seen, when the composition comprises any one of the comparative amines selected from a group consisting of N,N,disec-butyl-para- phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA), then efficiency for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene of the nitroxides is not improved. Therefore, in one embodiment, the present composition does not comprise any one of the amines selected from a group consisting of N,N,disec- butyl-para-phenylene diamine (UOP5), ethylene diamine (EDA), tetraethylenepentamine (TEPA), dipropyl amine (DP A), or diethanol amine (DEA). It may be noted that some of these amines result in very marginal improvement in efficiency of nitroxides, but same is not commercially viable.
It may be noted that, surprisingly and unexpectedly, with increase in concentration of amine, i.e. when about 20% or more of the amine is added to 4HT, the polymerization inhibition efficiency of present additive composition reduces marginally, the reasons for which are not know at present.
Accordingly, in view of above experimental data and analysis thereof, it can be concluded that only the additive compositions of the present invention comprising 4HT and amine selected from a group consisting of TIPA, THEED, Quadrol, TEA, TBA, MEA, OA and DBA, surprisingly and unexpectedly, result in improvement of control and polymerization inhibition efficiency of prior art additive composition consisting of 4HT, and these findings confirm synergistic effect of present compositions. Experiment 6:
The above Main Experiment was also carried out with round bottom reactor for prior art additive composition consisting of 4HT; and present additive composition comprising 4HT and TIPA, and it has been found that with addition of present amine additives, the efficiency of prior art additive composition to control and inhibit polymerization of styrene is, surprisingly and unexpectedly, generally improved even in round bottom reactor.
Table - VI
The above experimental data confirms the synergistic effects, and the surprising and unexpected technical effects and advantages of the additive composition of the present invention over the prior art additive composition and comparative compositions.
All of above findings confirm synergistic, surprising and unexpected effects of present composition at lower as well as at higher temperatures.
All of above findings also confirm that there is successive increase in efficiency of prior art additive to control and inhibit polymerization of styrene.
All of above findings also confirm that present composition is capable of achieving far better efficiency to control and inhibit polymerization of styrene with same dosage of the prior art additive, meaning thereby, the present invention results in economical and environmental benefits.
Above experimental results confirm that presently provided composition is far superior than prior art additive, and hence, has technical advantages and surprising effects over the prior art additive. It may be noted that the term "about" as employed herein is not intended to enlarge scope of claimed invention, but has been incorporated only to include experimental errors permissible in the field of the art.
Table V

Claims

Claims
Additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
(a) one or more of nitroxide (i.e. nitroxyl) compounds; and
characterized in that the said composition further comprises one or more of
(b) tertiary amines.
Additive composition as claimed in claim 1, wherein said amine is hydroxyl alkyl tertiary amine.
Additive composition as claimed in claim 1, wherein said amine is ethylene oxide treated amine.
Additive composition as claimed in claim 1, wherein said amine is propylene oxide treated amine.
Additive composition as claimed in claim 1 , wherein said amine is tertiary alkyl amine.
Additive composition as claimed in any one of the preceding claims 1 to 5, wherein said amine is mixture of one or more of hydroxyl alkyl tertiary amine, ethylene oxide treated amine, propylene oxide treated amine, tertiary alkyl amine.
Additive composition as claimed in any one of claims 1 , 2 and 6, wherein said hydroxyl alkyl tertiary amine is tris(2-hydroxypropyl)amine (TIP A).
Additive composition as claimed in any one of claims 1 , 3 and 6, wherein said ethylene oxide treated amine is Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxyethyl) ethylene- diamine) (THEED).
Additive composition as claimed in any one of claims 1 , 4 and 6, wherein said propylene oxide treated amine is Ν,Ν,Ν',Ν'-Tetrakis (2-hydroxypropyl) ethylene-diamine) (Quadrol).
Additive composition as claimed in any one of claims 1, 2 and 6, wherein said hydroxyl alkyl tertiary amine is tfiethanolamine (TEA).
Additive composition as claimed in any one of the preceding claims 1 , 5 and 6, wherein said tertiary alkyl amine is TrisfN-butylamine] (TBA).
Additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising:
(a) one or more of nitroxide (i.e. nitroxyl) compounds; and characterized in that the said composition further comprises
(b) one or more of amines selected from a group consisting of primary and secondary amines.
13. Additive composition as claimed in claim 12, wherein said primary amine is selected from a group comprising hydroxyl alkyl primary amine and alkyl primary amine.
14. Additive composition as claimed in claim 12 or 13, wherein said secondary amine is alkyl secondary amine.
15. Additive composition as claimed in any one of claims 12 to 14, wherein said hydroxyl alkyl primary amine is monoethanolamine (MEA).
16. Additive composition as claimed in any one of claims 12 to 15, wherein said alkyl primary amine is octyl amine (OA).
17. Additive composition as claimed in any one of claims 12 to 16, wherein said alkyl secondary amine is dibutyl amine (DBA).
18. Additive composition as claimed in any one of claims 1 to 17, wherein said composition comprises:
a) about 40 to about 99.75 % by weight of I) said nitroxide (i.e. nitroxyl) compounds; and
b) about 0.25 to about 60 % by weight of II) said amines, or mixture thereof.
19. Additive composition as claimed in any one of claims 1 to 18, wherein about 0.01 to about 2000 ppm of said composition is added to aromatic vinyl monomers stream based on weight of monomer.
20. Additive composition as claimed in any one of claims 1 to 19, wherein said nitroxide (i.e. nitroxyl) compound is selected from the group comprising di-tert- butylnitroxyl, l-oxyl-2,2,6,6-tetramethylpiperidine, l-oxyl-2,2,6,6- tetramethylpiperidin-4-ol, 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-one, and derivatives thereof; and di-nitroxides and derivatives comprising bis(l-oxyl- 2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(l-oxyl-2,2,6,6- tetramethylpiperidin-4-yl)succinate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4- yl)adipate, and mixture thereof.
21. Additive composition as claimed in any one of claims 1 to 20, wherein said nitroxide (i.e. nitroxyl) compound is selected from the group comprising bis(l- oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate and 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol or 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl (or 4 Hydroxy Tempo or 4-HT) , and mixture thereof.
Additive composition as claimed in any one of claims 1 to 21, wherein said nitroxide (i.e. nitroxyl) compound is 1 oxyl-2,2,6,6, tetramethylpiepridin-4-ol (or 4 Hydroxy Tempo or 4-HT).
Additive composition as claimed in any one of claims 1 to 22, wherein said composition does not comprise aromatic nitro compound.
A method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene by adding additive composition as claimed in any one of the preceding claims 1 to 23 to monomers stream, wherein said composition comprises:
(a) one or more of nitroxide (i.e. nitroxyl) compounds; and
characterized in that the said composition further comprises one or more of
(b) said amines; and
said composition is added to said monomers.
The method as claimed claim 24, wherein about 0.01 to about 2000 ppm of said composition is added to aromatic vinyl monomers stream based on weight of monomer.
A method of using additive composition as claimed in any one of the preceding claims 1 to 23 for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene, wherein said composition comprises:
(a) one or more of nitroxide (i.e. nitroxyl) compounds; and
characterized in that the said composition further comprises one or more of
(b) said amines,
and said monomers are treated with said composition.
The method as claimed claim 26, wherein said aromatic vinyl monomers stream is treated with about 0.01 to about 2000 ppm of said composition based on weight of monomer.
A method for preparing additive composition as claimed in any. one of the preceding claims 1 to 23 for controlling and inhibiting polymerization of aromatic vinyl monomers including styrene, wherein the method comprises: (A) mixing one or more of said nitroxide (i.e. nitroxyl) compounds, characterized in that said nitroxide (i.e. nitroxyl) compound or mixture thereof is further mixed with one or more of (B) said amines.
29. The method as claimed claim 28, wherein said one or more of nitroxide compounds, and said one or more amines are added to monomer stream individually.
30. The method as claimed in any one of the preceding claims 24 to 27, wherein said composition is used over a range of temperature varying from about 50 degree C to about 180 degree C.
31. Additive composition for control and inhibition of polymerization of aromatic vinyl monomers including styrene substantially as herein described and illustrated with the help of foregoing examples.
32. A method for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene substantially as herein described and illustrated with the help of foregoing examples.
33. A method of using additive composition substantially as herein described and illustrated with the help of foregoing examples.
34. A method for preparing additive composition substantially as herein described and illustrated with the help of foregoing examples.
EP12839189.3A 2011-12-02 2012-11-21 Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof Active EP2785780B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL12839189T PL2785780T3 (en) 2011-12-02 2012-11-21 Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN3383MU2011 2011-12-02
PCT/IN2012/000758 WO2013105113A1 (en) 2011-12-02 2012-11-21 Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Publications (2)

Publication Number Publication Date
EP2785780A1 true EP2785780A1 (en) 2014-10-08
EP2785780B1 EP2785780B1 (en) 2015-07-01

Family

ID=54257025

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12839189.3A Active EP2785780B1 (en) 2011-12-02 2012-11-21 Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Country Status (18)

Country Link
US (1) US9725649B2 (en)
EP (1) EP2785780B1 (en)
JP (1) JP5952914B2 (en)
KR (1) KR101625041B1 (en)
CN (1) CN104350095B (en)
AU (1) AU2012365382B2 (en)
BR (1) BR112014013283B1 (en)
CA (1) CA2857550C (en)
ES (1) ES2548553T3 (en)
MX (1) MX339245B (en)
MY (1) MY167439A (en)
PH (1) PH12014501142A1 (en)
PL (1) PL2785780T3 (en)
RU (1) RU2625300C2 (en)
SG (1) SG11201402792UA (en)
TW (1) TWI560203B (en)
WO (1) WO2013105113A1 (en)
ZA (1) ZA201404795B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2785780B1 (en) 2011-12-02 2015-07-01 Dorf Ketal Chemicals (India) Private Limited Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof
IN2013MU01165A (en) * 2013-03-26 2015-04-24 Dorf Ketal Chemicals India Private Ltd
KR102511957B1 (en) 2017-02-27 2023-03-17 에코랍 유에스에이 인코퍼레이티드 Antifouling agent for compressor
SG11201908734QA (en) * 2017-04-05 2019-10-30 Dorf Ketal Chemicals India Private Ltd Composition for control and inhibition of polymerization of monomers, and method of use and preparation thereof
WO2020205994A1 (en) 2019-04-02 2020-10-08 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4633026A (en) 1983-02-22 1986-12-30 Ethyl Corporation Process for preparing ring-halogenated vinyl aromatic monomers
JPS6413041A (en) * 1987-07-07 1989-01-17 Hakuto Kagaku Kk Agent for suppressing growth of polymer in olefin-production apparatus
FR2632638B1 (en) 1988-06-10 1991-04-19 Atochem PROCESS FOR THE MANUFACTURE OF AMINE OXIDES
US5290888A (en) * 1990-07-20 1994-03-01 Ciba-Geigy Corporation Process for stabilizing ethylenically unsaturated compounds and stabilized monomer compositions
KR100193146B1 (en) * 1990-07-20 1999-06-15 월터 클리웨인, 한스-피터 위트린 Stabilized Monomer Composition
US5254760A (en) 1992-07-29 1993-10-19 Ciba-Geigy Corporation Inhibiting polymerization of vinyl aromatic monomers
US5955643A (en) * 1997-10-17 1999-09-21 Nalco/Exxon Energy Chemicals, L.P. Composition and method for inhibiting polymerization during the anaerobic of styrene
US5910232A (en) * 1998-06-10 1999-06-08 Nalco/Exxon Energy Chemicals, L.P. Method for inhibiting polymer formation in styrene processing
DE69904848T2 (en) * 1998-09-09 2003-11-06 Baker-Hughes Inc., Houston INHIBITING THE POLYMERIZATION OF STYROL MONOMERS WITH SUBSTITUTED DIHYDROXYARENES AND NITROGEN OXIDES
CA2378122A1 (en) * 1999-08-18 2001-02-22 Maria Beata Manek Method of inhibiting vapor phase fouling in vinyl monomer systems
US6403850B1 (en) * 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6579442B2 (en) * 2001-05-22 2003-06-17 Ge Betz, Inc. Methods and compositions for inhibiting polymerization of vinyl monomers
US6525147B1 (en) * 2001-06-20 2003-02-25 Baker Hughes Incorporated Use of diamines and alkanolamines to inhibit unsaturated monomer polymerization
RU2243201C1 (en) * 2003-08-18 2004-12-27 Открытое акционерное общество "Нижнекамскнефтехим" Method for inhibition of polymerization process of vinylaromatic hydrocarbons
JP2005213369A (en) * 2004-01-29 2005-08-11 Hakuto Co Ltd Fouling prevention agent and fouling prevention method
BR112014012937B1 (en) * 2011-11-29 2020-04-28 Dorf Ketal Chemicals India Private Ltd amine-based additive composition for the control and inhibition of styrene polymerization, and method of preparation and use
EP2785780B1 (en) 2011-12-02 2015-07-01 Dorf Ketal Chemicals (India) Private Limited Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013105113A1 *

Also Published As

Publication number Publication date
MY167439A (en) 2018-08-28
JP2015500355A (en) 2015-01-05
PH12014501142B1 (en) 2014-07-28
PH12014501142A1 (en) 2014-07-28
EP2785780B1 (en) 2015-07-01
KR20140097265A (en) 2014-08-06
WO2013105113A1 (en) 2013-07-18
TWI560203B (en) 2016-12-01
PL2785780T3 (en) 2015-12-31
RU2625300C2 (en) 2017-07-13
AU2012365382A1 (en) 2014-07-24
AU2012365382B2 (en) 2015-01-15
CA2857550C (en) 2017-02-28
JP5952914B2 (en) 2016-07-13
TW201331234A (en) 2013-08-01
ZA201404795B (en) 2015-10-28
RU2014126229A (en) 2016-01-27
CN104350095A (en) 2015-02-11
KR101625041B1 (en) 2016-05-27
ES2548553T3 (en) 2015-10-19
BR112014013283B1 (en) 2020-05-12
US9725649B2 (en) 2017-08-08
CN104350095B (en) 2016-08-24
WO2013105113A4 (en) 2013-09-26
MX339245B (en) 2016-05-18
MX2014006406A (en) 2014-07-11
US20140364660A1 (en) 2014-12-11
CA2857550A1 (en) 2013-07-18
SG11201402792UA (en) 2014-06-27

Similar Documents

Publication Publication Date Title
AU2012364217B2 (en) Improved amine based additive composition for control and inhibition of polymerization of aromatic vinyl monomers, and method of use thereof
CA2858755C (en) Additive composition for control and inhibition of polymerization of aromatic vinyl monomers, and method of use thereof
US9334445B2 (en) Amine based additive composition for control and inhibition of polymerization of styrene, and method of use thereof
AU2012365382B2 (en) Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140627

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20150303

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SUBRAMANIYAM, MAHESH

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 733947

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150715

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012008473

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2548553

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20151019

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 733947

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150701

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151002

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151102

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151101

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012008473

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

26N No opposition filed

Effective date: 20160404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151121

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151121

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121121

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20171127

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20181121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181121

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CZ

Payment date: 20191118

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20201104

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211121

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231126

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231201

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20231122

Year of fee payment: 12

Ref country code: FR

Payment date: 20231127

Year of fee payment: 12

Ref country code: DE

Payment date: 20231129

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231127

Year of fee payment: 12